Floor polish composition



United States Patent 3,406,133 FLOOR POLISH COMPOSITION Jack HenryHartshorn, Springfield, Pa., assignor to E. I. du Pont de Nemours andCompany, Wilmington, Del., a corporation of Delaware No Drawing. FiledOct. 30, 1964, Ser. No. 407,871 9 Claims. (Cl. 260-285) ABSTRACT OF THEDISCLOSURE This invention comprises an aqueous emulsion floor polishhaving to 30 parts by weight of leveling resins, 5-60 parts by weightwaxes, and 35-90 parts by weight of a terpolymer of (a) a conjugateddiene (b) an a ti-U11- saturated carboxylic acid containing 3-9 carbonatoms and (c) a monomeric composition consisting essentially of at least50% of a lower alkyl ester of a C to C a,,6- unsaturated carboxylicacid. The weight proportions of (a), (b) and (c) are in the percentageranges of 4-49, 1-15, and 36-95, respectively. These emulsions providefloor polishes which form nonyellowing high gloss films with excellentmar and scuff resistance properties.

This invention concerns an aqueous emulsion polish composition and moreparticularly a polish composition having improved durability and colorcharacteristics.

Many types of floor polishing compositions are known including thosethat require buffing and those that dry to a bright luster withoutbuffing. Of the former types are the well known wax compositionsgenerally containing large proportions of expensive carnauba wax. Thepolishes in the latter category, known as dry-bright polishes, aregenerally available as aqueous emulsions of waxes and certain polymericmaterials. Several polymeric materials have been used in emulsionpolishes, the most common among these being polystyrene. Polystyreneemulsion polishes, while producing a hard surface, show littleresistance to pock marking by high heels and demonstrate appreciableyellowing on aging and significant discoloration on successive polishapplications. Other common floor polish compositions, such as mixturesof acrylic polymers are quite soft, thus readily picking up dirt andrubber heel marks.

According to the present invention, there is provided in an aqueousemulsion floor polish comprising 5-30 parts by weight levelling resinsand 5-60 parts by weight waxes, the improvement, in combinationtherewith, comprising essentially 35-90 parts by weight of a terpolymerof (a) a conjugated diene represented by the structural formula,

wherein R and R are individually hydrogen, chlorine, fluorine, or loweralkyl groups, (b) an a,B-unsaturated carboxylic acid containing fromthree to nine carbon atoms, and (c) a monomeric composition consistingessentially of at least fifty percent of a lower alkyl ester of a C to Ca, 3-unsaturated carboxylic acid. The portions (a), (b), and (c) are inthe weight percentage ranges of 4-49, 1-15, and 36-95, respectively, theterpolymer being in the form of a latex with a maximum particle size of0.2 micron in diameter. The emulsion polish of this invention whenapplied to floors, such as linoleum, asphalt, vinyl asbestos, or vinyland rubber, yields a hard, nonyellowing high gloss film with excellentmar and scufi resistant properties. In addition, the polish may beremoved, for rewaxing, or additional wax may be applied without theheretofore characteristic yellowing.

Due to their easy availability, the preferred conjugated dienes of theterpolymer are 1,3-butadiene, isoprene, and

ice

chloroprene. Other useful conjugated dienes are2,3-dichloro-1,3-butadiene, fluoroprene, 2,3-difluoro-1,3-butadiene,2,3-dimethyl-1,3-butadiene, 1,3-butadienes with lower alkyl groupssubstituted on one or both of the 2,3-carbon atoms. As used in thisinvention the term lower alkyl group refers to alkyl groups containingless than about seven carbon atoms (i.e., about 1-6 carbon atoms). Thelower alkyl groups can be the straight chain alkyl groups, such asmethyl, ethyl, propyl, pentyl, hexyl and in addition, all branchedisomers thereof (e.g., isopropyl, sec. butyl, tert. butyl, neopentyl,etc.).

The preferred a,fl-unsaturated carboxylic acids utilized to form theterpolymer of this invention are acrylic acid and methacrylic acid.Additional useful acidsare those having the structure:

R3 0 r H ll HC=C-COH where R is a lower alkyl group. Such acids as ethylacrylic acid, propyl acrylic acid, butyl acrylic acid, etc. can be used.

The lower alkyl ester used in preparing the terpolymer of this inventioncan be formed from any of the carboxylic acids set forth in the previousparagraph. Useful esters are those having the structure:

where R, is hydrogen or a lower alkyl group and R is a lower alkylgroup. The acid component of the ester is not dependent upon thecarboxylic acid used in the terpolymer', thus, methyl methacrylate canbe the lower alkyl ester while acrylic acid is the a,/S-unsaturatedcarboxylic acid. The lower alkyl methacrylates and lower alkylacrylates, such as methyl acrylate, methyl methacrylate, ethyl acrylate,ethyl methacrylate, etc., are the preferred esters.

Though this invention concerns a terpolymer prepared from the abovemonomers, namely, (a) a conjugated diene, (b) an c p-unsaturatedcarboxylic acid, and (c) a lower alkyl ester, a vinyl unsaturatedmonomer can replace up to fifty percent of the lower alkyl ester (c).Thus, it is to be understood that the monomeric composition (c), usuallyreferred to as the ester composition, can contain up to fifty percent ofother compounds, such as acrylonitrile, styrene, substituted styrenes,vinyl ethers, vinyl alcohols, vinyl esters and lower alkyl derivativesof these compounds.

Generally, the weight percentage ranges of diene, acid, and ester are4-49, l-15, and 36-95, respectively, but the preferred ranges will varywith the particular diene used. Representative examples of terpolymerweight percentage ranges are:

The terpolymer latex can be formulated by any aqueous emulsionpolymerization technique. These techniques in which the monomers aredispersed in water with anionic or a combination of anionic and nonionicsurfactants and free radical catalysts are well known in the art. Thepolymerization which is believed to go to about completion isaccomplished at a temperature ranging from below room temperature to theboiling point of '3 water and apressure of up to 100 lbs./ sq. in. Athorough discussion of useful emulsion polymerization processes can befound in the book Emulsion Polymerization by F. A. Bovey, I. M.Koltholf, A. I. Medalia, and E. J. Meehan, published by IntersciencePublishers in 1955.

In formulating the terpolymer latex, polymerization conditions arecontrolled to provide a polymer average particle size that does notexceed two-tenths of a micron in diameter, all particles beingconsidered practically spherical. Larger average particle sizes willresult in polishes with rough surfaces and milky appearances. Forbest'results, the particle size is maintained at less than one-tenth ofa micron in diameter and the particles are of uniform size. To formulatethe floor polish composition of this invention, a terpolymer latex ofthis invention is combined with conventional floor polish components.The term conventional floor polish components as employed herein meansany of those components known in the art and used as major components infloor polish compositions. This includes mixtures of levelling resinsand waxes, and optionally as minor additions, compounds serving ascoalescing aids, plasticizers, surfactants, and such other materials aswill improve esthetic, preservative, or application properties.

In a floor polish composition alkali soluble levelling resins are used.Examples of some of the more common of these are: (a) high acid numberrosins, rosin maleate adducts, and their esters; (b) high acid numberphenolics and their esters; (c) shellac and modifications thereof; (d)styrene 'maleic copolymers and their esters; and (e) high acid numberpolyesters. In particular, a pale, high melting alkali soluble resincalled Shanco L-1177, made by Shanco Plastics and Chemical, Inc., can beused effectively. This levelling resin is characterized by a meltingpoint (R. & B.) of 173-183 C., an acid num ber of 185-195, and anammonia requirement (28%) of about based on the resin.

Waxy materials, another preponderant ingredient of conventional floorpolish compositions, usually comprise natural or synthetic waxes orblends thereof. Examples of useful, natural waxes are carnauba, sugarcane, bees wax, and montan. Synthetic waxes, such as microcrystallineparatfin and polyethylene can be used. The polyethylene wax can beoxidized, unoxidized, or emulsion polymerized, suitable examples ofwhich are Allied Chemicals #629 polyethylene or PolyEm of SpencerChemical. For addition to floor polishes, these waxes are dispersed inwater with surface active agents, such as sorbitol condensate adducts,polyglycol ether products, alkali or amine salts of fatty acids,sulfates, and sulfonates.

Optional minor ingredients in floor polish compositions includecoalescing aids, plasticizers, and surface active agents. Commoncoalescing aids are high boiling alcohols and their ethers, such asethylene glycol, diethylene glycol, and Carbitol. Plasticizers commonlyemployed are the alkyl phosphates and phthalates, particularlytributoxyethyl phosphate and dibutyl phthalate. Anionic surfactants,such as sodium lauryl sulfate and morpholine oleate and nonionicsurfactants, such as sorbitol condensates and polyethylene oxide adductsare also commonly added in the conventional floor polish composition. Inaddition, fluorocarbon surface active agents, as set forth in UnitedStates Patent 2,937,098, can be used.

The polish composition of the present invention is prepared by dilutingthe major ingredients of the cornposition, namely the terpolymer latex,levelling resin,

4 and wax to about the same solids level and mixing. In the resultingcomposition, the Weight ratios of the solids are generally in theproportion of 35-90 parts terpolymer, 5-30 parts levelling resin, and5-60 parts wax. The most useful ratio is dependent upon the particularmajor ingredients included as can be seen in Examples I-IV. Otheroptional constituents of conventional polishes can be admixed therewith,with or withoutprior dilution, as desired. It is customary to dilute thecompositions to a solids concentration of 5% to 30% by weight. Thepreferred solids concentration range for producing good results, ease ofapplication, and low cost is 10% to 20% by weight. Conveniently, theterpolymer latex is diluted directly with water to the desired solidslevel, but, the levelling resin is commonly dissolved in an aqueousalkali solution, such as ammonia, and the wax, as stated before, isdispersed in water with a surfactant.

Tests were conducted comparing the floor polish composition of thisinvention with commercially available household fioor polishes. However,it is to be understood that the floor polish of this invention is notlimited to use on household floors, and can be used on other flooring,such as industrial. In the following tables, Compositions A and B referto polishes of the present invention, as given in Examples I and IIbelow, containing 1,3-butadiene, methacrylic acid, andmethylmethacrylate diluted to 15 and 18 percent solids, respectively.Compositions C, D, and E represent commercially available householdfloor polishes; C being a predominantly acrylic polish, D being apredominantly polystyrene polish, and E being a styrene-acrylic polish.

The yellowness index test determines the tendency of a floor polish todiscolor or turn yellow on successive polish applications. The testprocedure is to dip coat for 30 seconds, No. 4 whatman filter papers inthe test polishes and allow them to dry at 77 F. and 50% relativehumidity for at least three hours. The yellowness index is determined ona modified Gonio multipurpose photometer by obtaining reflectance valueson the treated papers employing three different optical filters andusing the following formula:

Reflectance (amber)- reflectance (blue) Reflectance (green) Yellownessindex X Higher yellowness index values indicate greater degrees ofyellowness. Table I presents the results of these tests.

TABLE I.YELLOWNESS INDEX TEST Low temperature flexibility tests wereconducted to compare resistance of the polishes to permanentdeformation. Greater flexibility indicates higher resistance topermanent deformation, such as pock marks inflicted by high heels. Inthis test 0.2 mil of polish is spread over a 2" by 4" area ofhomogeneous vinyl tile by means of a doctor blade applicator and allowedto dry. The test panel is conditioned at approximately 40 F. for aminimum of three hours and is then inwardly bent around a 1" diametermandrel which has similarly been cold conditioned. The panels are ratedfor comparative lack of cracking or crazing in the film or actualseparation of the film from the panel. Table II presents the results ofthese tests:

TABLE II.LOW TEMPERATURE FLEXIBILITY TESTS Floor Polish Composition A BC D E Flexibility Excellent (2)... Excellent (1)-- Excellent (2).-..Poor (Film Separation)" Fair-Good (Severe Cracking);

No'rE.-Numbers (in parentheses) indicate order of preference where twoor more products are rated the same. (1 being preferred over 2).

3,406,133 6 Heel mark resistance tests were conducted by randomlyEXAMPLE IV tumbling rubber heels onto 9" by 9" standard fioor tilepanels in a soil capsule developed by Foster D. Snell, Inc. The soilcapsule is a box with the test panels strapped to Dispersion orsolution, parts Terpolymer latex (aqueous emulsion 18% solids):

the insides. The rubber heels are placed inside the capsule r 24%isoprene. 5% methacrylic acid, 71% methyl and the capsule is rotated forseveralminutes inside the methacrylate 0 capsule and the capsule isrotated for several minutes Levelling resin! G- q ammoniaafter which thepanels are examined. The method of this e n) test is more clearly setforth in a paper titled A Method WaX1 Y (emulsion polymerized V forEvaluating Heel Mark Resistance by B. Berkeley and Q 15 W. J. Hackett,published in the Proceedings of the 50th 10 p t l solvent 2 Mid-YearMeeting of the Specialty Manufactures Associ- Plastlclzel yethylphosphate) 0.5 ation, May 1964, Chicago, Ill. The ratings obtained inThe resulting composition of Example IV has less of this test arePresented in Table III! a tendency to yellow than any of the previousexamples TABLE IIL-HEEL MARK RESISTANCE TEST Floor Polish Composition AB C D E Ofiicial'lest-Asphalt V. Good (2)-.. Excellent (1).-- V. Good 1Good E Ofiicial Test-Vinyl Asbestos Ex ll nt Good Fair-Good V. $523318?Nor)E.-Numbers (in parentheses) indicate order of preference where twoor more products are rated the same. (1 being preferred over 2 Thefollowing Examples I through IV illustrate the and maintains equivalenthardness to the other examples. floor polish compositions of thisinvention. All quantities 25 What i l i d i of terpolymers, levellingresin, and wax are on a parts 1. In an aqueous emulsion floor polishconsisting esby weight basic of solids plus diluent. The ingredientssentially of 5-30 parts by weight levelling resins and 5- as set forthin the examples are cold blended by conven- 60 parts by weight waxes,the improvement, in combinational mixing means to form the polishcomposition. tion therewith, consisting essentially of -90 parts byweight of a terpolymer of (a) a conjugated diene repre- I EXAMPLE sentedby the structural formula,

Dispersion or solution, parts Terpolymer latex (aqueous emulsion 15%solids):

15% 1,3-butadiene, 5% methacrylic acid, 80%

methylmethacrylate 75 35 g Levelling resin: Shanco L-l177 (aqueousammonia-15% resin) 15 Wax1: d PolyEm-IO (emulsion polymerized 15% 10wherein R1 and R2 are Selected individually from the csgitsgl Solvent 20 4O groulri clonsisting of hydrogen, chlorine, fluorine, andlowplasticizer (tributoxyethyl phosphate) 0 3 er a y groups (b) an rfi'carboxyhc acid containing from three to nine carbon atoms, and (c) amonomeric composition consisting essentially of at least The compositionof Example I is represented by (A) y Percent Of a lower alkyl ester of aa t0 9 sl n-Octanol solvent 0.1

in Tables I through III presented above. aturated CaFbOXYIiC acid,wherein and are EXAMPLE H 1n the weight percentage range of 4-49, 1-15,and 36 I 95, respectively, said terpolymer being in the form of aDispersion or solution, parts latex and having a maximum averageparticle size of Telpolymer latex (aqueous emulsion 18% solids): lessthan 0.1 micron in diameter.

15% 1,3-butadiene, 5% methacrylic acid, 80% 2. The aqueous emulsionpolish of claim 1 in which methylmethacrylate 70 is a lower alkyl esterand wh rei (b the a Levelling resin: Shanco L-1l77 (aqueousammosaturated carboxylic acid, and (c), the lower alkyl ester nia-18%resin) 15 have the structures: Wax: PolyEm-lO (emulsion polymerized 18%solids) 15 Carbitol solvent 2 R3 0 R4 0 x th h s ha H Plastrcizer(trrbuto ye yl p o p te) 05 HC=(E (||J OH and I g 5 The composition ofExample II is represented by (B) in Tables I through III presentedabove.

EXAMPLE 111 respectively, with R and R individually selected fromDispersion or solution parts the l p ting of hydrogen and lower alkylgroups Terpolymer latex (aqueous emulsion 15% solids): and R5lsaloweralkylgrqup' 27.5% chloroprene, 5.0% methacrylic acid, 67.5% The aquequsemulslon Pollsh of clalm Wi methylmethacrylate 75 the alkyl ester 13Selected m the group consisting of Levelling resin: Shanco L-1177(aqueous ammolower alkyl methacrylate? and 9 alkyl acrylatesnia 15%resin) 15 4. The aqueous emulsion pol1s h of claun 2, wherein Wax:POIYEm loaa (emulsion polymerized 15% the a,[3-unsaturated carboxyhcacid is selected from the 801i n 10 group consisting of acryl c acid andmethacrylic acid. Plasticizer (tributoxyethyl phosphate) 8 l aquwllselflulslon p h f dam 2, wherein Carbitol solvent 2 0 the conlugateddlene 15 ted flOm the group consisting of 1,3-butadiene, chloroprene,and isoprene.

The resulting composition of Example III gives results 6. The aqueousemulsion polish of claim 5, wherein comparable to those of thecompositions given in Exthe a,fi-unsaturated carboxylic acid is selectedfrom the amples I and II with respect to the hardness tests and hasgroup consisting of acrylic acid and methacrylic acid.

a slight tendency to give a higher yellowness index value. 7. Theaqueous emulsion polish of claim 6, wherein 7 the alkyl ester isselected from the group consisting of l References Cited lower alkylmethacrylates and lower alkyl acrylates. UNITED STATES ATENTS 8. Theaqueous emulsion polish of claim 5, wherein 3,202,627 8/1965 Van 'Ess eta1. 260-807 the u,;3-unsaturated carboxylic acid is methacrylic acid andthe alkyl ester is methyl methacrylate. 5 3,234,158 2/1966 Pfiungel260-285 9. The aqueous emulsion polish of claim 8, wherein 2,883,3554/1959 Balfe the conjugated diene is 1,3-butadiene and the diene, acidand ester are in the weight percentage ranges of 4-35, LI FROME P'lmaryExamine" 2-10, and 55-94, respectively. H. S. KAPLAN, AssistantExaminer.

